Control of endothermic and exothermic catalytic reactions



May19, 1942. K Y c. l.. THOMAS 2,283,832

l CONTROL- AND EXOTHERMIC CATALYTIC REACTIONS I Filmfan. 9, 1940 Illrll 1111111;

32,265 HEATER? t thermic reaction zone.

Patented May 19, 1942 UNITED STAT ES v 'PATENT OFFICE rnEaMrcoA'raLrrrc aaaorroNs Charles L. 'lliomaav Chicago, lll., assignor` to Universal 'Oil Products Company, Chicago, lll., a v corporation of Delaware 1 application' Febreary 9. 1 940, serial No. :5,113,098

condensing fluid is employedas the heat trans-- mits-1)' place for `a substantial body or pool of liquid in which, according to conventional practice, said tubes or other elements are immersed or bathed. Preferably, in accordance' with the provisions of the present invention, any of the liquid heat transfer' medium which remains unvaporized in owing over the surface'of the catalyst container in which the exothermic reaction is taking p1ace,as well as the condensate which. forn is on the surface ofthe catalyst 'container in which the endothermic reaction is'taking place, ilows accumulating drum or the like wherefrom it is' from the lower portion of the reactor to a small pumped back to the reactor and sprayed or oth- 'container in which Jthe exothermic reaction is fer medium, is to employ separate interconnected reactors of-the heat exchanger type eachcontaining tubular elements or'the `like'wherein the desired conversion reaction takes place, the tubular elements wherein the exothermic reaction is tak,- ing piace being .disposed in a body of liquid which is vaporized by the heat evolved. the vapors thus generated being conducted to the other reactor wherein they are condensed by contact with the tubular elements wherein the endothermic reaction is taking place and the condensed liquid being returned therefrom to the body of liquid in the first reactor,

,The present invention obviates the use of separate reactors inv this type of system'by dispos-y ing the tubes or other elements wherein the enplace with the heat transfer liquid which is thereerwise distributed overthe surface of the catalyst taking place.` Thus, when-the operation is discontinued for anyv reason and the circulatingl lpump is stopped, the liquid drains to the accumulator, leaving the reactor substantially dry. This is particularly advantageous when a heat transfer fiuidwhich solidifies at normal temperature is employed, since, by the elimination of a body of such'material in the reactor, its solidification therein and the attendant diillculties are.

' obviated. Thus, the reactor may be Areadily opened for inspection, repair or the like, after the operationisdiscontinued andthe apparatus is cooled, and in order to melt the heat transfer material in preparation for starting the operation, it is only necessary to supply ,-heat exdothermic and exothermic reactions occur within ternally. or otherwise. ,to vthe relatively small.

. mass of such material in the accumulator..

The invention is adapted to be advantageously utilized for controlling temperatures in awide variety of catalytically promoted orcatalytically by vaporized and condenses on the surface ofthe zone in which the endotherniic reaction is taking place. This also obviates maintaining a substantial body or a pool of liquid about the zone where'- lin the exothermic reaction occurs and is particularly advantageous in operations wherein the i -zones of endothermic and exothermic reactions are periodically shifted from one set of tubes to another, since the shift may be accomplished without'transferring a substantial body or pool -of liquid from one reactor. to another.

retarded reactions and although, as previously explained, it is particularly advantageous as applied to simultaneously conducted endothermic `and exothermic reactions of the class in which the zones ofxendothermic and exothermiereaction are periodically shifted, it is not limited to catalytic reactions so long as the operation in,- volves the transfer of heat from a zone wherein it is liberated' to one in which it is absorbed i through the medium of a vaporlzing and condensing vfluid employed in themanner herein procapacity is materiallytreducedI by virtue of the t substitution of a sheet orillm of4 evaporating liquid on the surface of the tubes or other elements wherein the exothermic reaction takes The most common example of an operation of the general type inwhich the zones' of endothermic and exot-hermic reaction are periodically shifted, is one in which the activity of a mass of catalytic material employed to promote or re,- tard one` of the reactions decreases with such rapidity and to such an 'extent that frequent hydrogenation are examples of other exothermic' reactions which may comprise the exothermic step of a process embodying the features provided by the invention and in such instances the endothermic step may comprise, forA example, pre- The catalytic and in which the improved process of the invention may be conducted. The shell of the reactor is illustrated in cross-section and other portions of the apparatus are shown in elevation.

Referring to the drawing, the outer shell I of the reactor. in the particular case here illustrated, is cylindrical in form and is provided with an upper head 2 and a lower head1. I'he interior of the shell is divided into compartments, A-and A', B and B',C, D and D' by means of the horizontal partitions l and 5, the lower substantially cone-shaped partition 6 and the vertical partitions 'I and 8. An inlet nozzle 9 in the VUpper head 2 communicates with compartment heating of the reactants forl the exothermic step,

the generation of steam, the heating or vaporization of oil or any other fluid for any desired purpose or it may comprise a pyrolytic or catalytic conversion reaction such as thermal or catalytic cracking, dehydrogenation, isomerization, cyclization or the like or a combination of such operations. These examples are typical of conversion operations encountered in modern hydrocarbon oil renning. The invention will find further application in many other chemical industries andgits broad features are in no way limited to the s'peciilc reactions involved.

Any heat transfer medium may be employedl which will substantially vaporize at 'a temperature within the range of that desired for the exothermic reaction and 'which will be substantially condensed at a temperature within the range suitable for conducting the endothermic reaction. Atmospheric or substantially atmospheric pressure may be employed in the zone wherein vaporization and condensation of the heat transfer medium employed occurs, or, when required, the

' boilingpoint of the heat transfer medium employed may be modified by the use of sub-atmospheric-or superatmospheric pressure in this zone. The specific heat transfer medium employed in any given case may be selected to fulll the above requirements and may range from relatively low-boiling liquids or readily condensible normally gaseous materials such as propane, water, alcohol and the like through the many heavier liquids such as hydrocarbon oils, aliphatic and aromatic ethers and glycols to and including normally solid materials such as molten salts and mixtures thereof (eutectic or otherwise) low` melting point metals and alloys. Wherever possible, theheat transfer medium selected should be non-corrosive and otherwise chemically inert to metals which are not injured by and exert no detrimental effect on the endothermic and exothermic reactions involved but, when no heat transfer medium which fulfills all of these requirements is available,- the shell and tubular elements or catalyst containers of the reactors may be constructed of a metal or an alloy which is not adversely effected by a heat transfer medium which possesses the required physical characteristics, while the tubes or other elements of the reactor, which form the zones wherein'thc endothermic and exothermic reactions occur, may be coated or lined `with another suitable metal, alloy or other protective coating which does not; adversely affect and is not adversely A and compartments A and D communicate through the tubular elements I0 extending therebetween, an outlet nozzle II in the lower head 3 communicating with compartment D. On the opposite side of a vertical planepassing through partitions] and 8, an inlet nozzle S'in the upper head communicates with compartment A' and the latter communicates with compartment D' through the tubular elements I0 exl or the liquid from zone B' over the surface of vto 1s obtained. 1

tubes III'. whichever tubes comprise thezone in which the exothermic reaction is taking place, as will be later explained. i

Vapors generated on the surface of the zone in which the exothermic reaction is taking place are totally or partially condensed on the surface of the zone in which the endothermic reaction is taking piace. Thus, an emclent transfer of heat4 endothermic reaction from the exothennlc to the Condensate formed on the surface of the zone in which the endothermic reaction is taking place islremoved from the lower portion of the reactor through line I3, together with any quantity of vapors generally in excess of those required to supply the desired heat to the endo# thermic reaction.- When only liquid condensate is thus removed from the lower portion of the reactor, it may be supplied from line I3 4through line I4, valve I 5 and line I9 to accumulator 2li or it may be passed, all or inl part, from line I3 through valve IB, cooler I 1, line I 8 and valve I9 to theaccumulator. In case vapors are with-H drawn with the liquid from the reactonthe mixture is preferably passed, as' above described, through cooler I1 to the accumulator.

' The function of coolerl II is to 4condense any .vaporous components of the convective medium removed from the reactor and to reduce the affected by the reactants and the catalyst,`in case a catalyst is employed.

The accompanying drawing diagrammatically illustrates one specific form of apparatus embodying the features provided by the invention temperature of the convective medium, when this is required. It may be of any suitable conventional form and, in the particular case here illustrated, comprises a heat exchanger to which suitable cooling fluid is directed through line `2I, passes through the cooler in indirect heat exchange relation with the convective medium and is removedtherefrom through line 22. Thus.

only liquid is collected in the accumulator and' is preferably kept at such a temperature that it may be returned therefrom to the reactor and sprayed over the surface of the tubularelements coil 30.

.' evolved in the exothermic reaction.'

in which the exothermic reaction is taking fplace l I1 and valve l5 in by-p'assq-line Hf or by adjustment of the amount and/or temperature of 'cooling fluid passed through cooler I1. V

' Liquid from accumulator 20 is directed through line 23 to pump 24 wherefrom itis fed through,

line 25 andit may ordinarily be directedwtherefrom, all or in part, through line `28 and Avalve 21 back to zone B or to zone'lBy without additional heating or cooling. However, in case additional heating of the recirculated convective liquid is required to obtain a closer approach to its vaporization point lnzones y13 and B', without allowing any appreciable quantity of vapors to collect in the accumulator, all or aregulated portion of the convective `liquid-'is recirculated to zones B and B' through heater 2l by manipulatingl valve 21 in line 2t, valve 29 in line 25 and'valve 23 in line'32. "From the .junction oflines 32 and 28,jthe reheated or u nreheated liquid fromaccumulator 20 is direct- -ed through line 34 and valve 35 to zo'n'e'B orl through line 3l' and A35' to zone B' and -from zone B or zone B', as lthe case may. be, itis again caused to pass' 4over the surface of the vtubular elements in which the exothermic reac- 'tionis taking place.

line 2i, although this is not illustrated in the drawing. q 'l -Theftubes Il andthe tubes Il' arate zones in which contact material such'as a `catalyst for promoting the de's'ziredv reaction may bev disposed and in which the'desiredfendotherj mic reaction andexothermic reviviilcation of the l accomplished with a relatively small quantity Heater 28 maybe of any suitable conventional form and, in the particular case here illustrated,

comprises a heating coil 30 disposed in a s uitable furnace 3I to which a regulated quantity catalyst may be alternately conducted. Any suitable means of conventional form maybeemployed for switching the ilow of the stream "of reactants and reactivating gasesl with respect to zones A and A and the separate tube banks and for diverting the outgoing reaction products and partially spent revivifying gases from zones D and D', each to the desired subsequent equipment. The specific form of such means 'employed do not Jconstitute part of the invention Vand since several suitable forms are nowwell vaporlzation and the latentfheat of` condensation. of a circulating heat transfer fluid for controlling `the temperature of simultaneously conducted endothermic and exothermic reactionsiand that, with the apparatus provided, this may be of heat transfer-'fluid and without maintaining a substantial bo'dy or pool of vaporizing heat transfer liquid about the zone in which the ex- 'othermic reaction is taking place, thereby accom- 35.' .of fuel and air are, supplied throughburner 3l to 'generate hot combustion gases4 inv-the i'ur- 'A nace and supply the desired quantity of heat therefrom to the convective fluid passing through Instead of ,serving as a temperingzone wherein any required small additional quantity of heat may besupplied to the convective liquid recirculated from the accumulator to zones B and B',

' heater28 may, in accordance with another mode of operation of 'the process, serve as a zone wherein a regulated quantityoi the recycled l convective liquid may beA revaporized at substantially the temperature prevailing'in space y C of the reactor and supplied to the latter zonel to augment, to any ldesired degree, the quantity of vapors evolvedfrom the convective liquid on the surface of the zone in which the exothermic' reaction is Ataking place. 'When this -mode of operation is employed, regulated quantities of;

the liquid from accumulator 20 are directed Y they endothermic reaction lis takingplace, supply to the latter any-heat required for conducting-'the endothermic reaction in excess of that In caseA heater 28 is utilizedv inthe manner last described and it is also necessary to supply some additionalheat to the convective liquid recirculated from Athe accumulator to zones B the description' of` the'drawing. -Furthermore, the process adaptsitself-to operations of the type in whichv the zones of .endothermic and simple form.

.It wm be understood, of course, that the se# companying 4drawing illustrates only one of the .many specific forms of apparatus in which the improved process provided bythe invention may be conducted and should, therefore, not be construed as a limitation. For example, insteadv of comprising tubes, the zone in which the endothermic and exothermic reactions occur'may'be formed between spaced metallic 'sheets 'or plates of any desired contour and any other well known means of spraying or otherwise distributing the heat transfer liquid over the surface upon which it is vaporized by heat evolved in the exothermic reaction may beemployed within the scope of the invention in place of the specific means illus-I trated in the,y drawing. Also, -either up-flow or down-flow may becemployed within .the "zones wherein the endothermicand exothermic reactions occur and the direction of flow isnot necessarily-the, same in both zones. For example, an

endothermic reaction such as dehydrogenation,

catalytic cracking or the likemay beaccom plished by passing a stream of heated hydrocar` e heat transfer fluid flowing downward over the and B', a. separate heater of any conventional form suitable for supplying the required additional heatv to the convective liquid recirculated to the zones B and B' is preferably provided in outer surface of the walls of this zone, while the catalytic material in the zonefof exothermic reaction is being reactivated by passing a stream of hot oxygen-containing gases downwardly through this zone in contact with the catalyst, concurrent to the film or sheet of vaporizing heat transfer uid flowing downwardly over the comprise sep- N cycle.

Aof oil cracked per hour.

exterior surface of the walls ofv this zone,` or, when desired, this procedure may be exactly reversed or concurrent or countercurrentow, with respect to theillms `or sheets of heat transfer fluid ilowing downwardly over the surface of the walls of theexothermic and endothermic 4reac- `tion zones may be employed in both zones. As applied to the apparatus illustrated in the drawing, this means that nozzles Il and Il' may be employed as inlet rather than outlet connections, while` nozzles 9 and 9' are employed as outlet rather than inlet connections or their usel as inlet and outlet connections may be alternated. As an example of one speciiic operation of the process provided by the invention as applied tov `the catalytic cracking of Ahydrocarbon oil (the l endothermic reaction) with .periodic vreactivation of the catalyst (the exothermic reaction)as it may be conducted in an apparatus of the characterillustrated, we will assume that the catalyst employed comprises preformed granules-or relatively small pellets 'of substantially uniform size and shape consisting essentially of alumina, silica and zirconia in the proportion of approximately 100 mols of ,SiOz to 2 mols of A120: to 5 mols of- ,ZrOa We will also assume that the oil to be cracked is `substantially completely vaporized and heatedto a temperature of approximately 950 .F. -prior to its contact with the active cracking catalyst and that, in addition to theheat thus supplied to the oil, an additional 250 B. t..u.s per pound is required to effect the desired cracking reaction in contact with the catalyst. `We will further assume that approximately 2% by weight A ,of the oil is converted to heavy carbonaceous ma terial which is deposited on the catalyst andthat approximately 290 B. t. u.s per pound of oil cracked are evolved during reactivation of the' catalyst, reactivation being accomplished by passcatalyst is so conducted that the average temperature in the catalyst bed during reactivationV is approximately 1050 F.- The mercury is supplied to the zone of the reactor from which it is sprayed over the surfaceof the tubular elements in which the exothermic reaction is taking place at a temperature of approximately 980 F. and a superatmospheric pressure of approximately 2501` `pounds per square inch is employed `in the mercury vaporizing and condensing space of the reactor. At this pressure, the mercury vaporizes ata temperature of approximately 1000cl F. yThe circulating pump is operated at such a rate that approximately 227 pounds per hour of mercury are circulated through the system per 100 pounds This figure is derived by dividing the heat evolved during regeneration, per 100 pounds of oil cracked,` by the heat o! vaporization of mercury which is approximately 127.5 B. t. u.s per pound (i. e., 29,000 divided by 127.5V equals 227+). However, when we divide ,the B. t. u.s required to crack ,100 pounds of oil by the heat of condensation of mercury, we lind that only about 196 pounds per hour of mercury vapor need be condensed on the surface' of the tubes in which the cracking reaction is taking place to satisfy the heat requirements `(i. e., 25g000 divided by 127.5 `equals 196+). Therefore, no liquid/mercuryis allowed to accumulate in the` reactor` and approximately 31 pounds per hour of mercury vapor is passed with the liquid mercury from the reactor through the condenser tothe accumulator, the mixture of mercury vapor and liquid being cooled in the condenser to such a temperature that, allowing for radiation losses in the recirculating lines, the resulting liquid mercury is returned to the reactor at a temperature of about 980 F.

The figure above given for the pounds of mercury circulated through" the system per 100 Vpounds of oil treated per hour is not to be taken as indicative of the quantity of mercury required within the system, since the rate of circulation preferably is relatively high so that the total mercury required within the system 4may be, for example, only fio to lo@ or less of the iigure above given (i. e., approximately 2 to 20 pounds l.

having heat-conductive walls, comprising the steps of `contacting a heat transfer medium in the form of a flowing film or sheet of liquid at a` temperatureclosely approaching its vaporization point with the heat-conductive walls of said exothermic reaction zone to substantially vaporheat content of said vapors is controllably increased prior totheir contact with said walls of the endothermic Vreaction zone. J

3. The method denedin claim 1, wherein the heat content of said vapors is controllably increasedprior to their contact with said walls of the endothermic` reaction zone by commingling a regulated additional quantity of hot vapors of A said heat transfer medium therewith.

4. The method defined 1n claim 1, wherein a regulated quantity of said evolved vapors are prevented from contacting and condensing on said walls of the endothermic reaction zone.

5. The method deiinedv in claim ,1, wherein a regulated quantity of` said evolved vapors are .prevented from contacting and condensing on said walls of the endothermic reaction zone, said lregulatedquantity of vapors being separately condensed and the resultingeondensate returned with the other liquid components of said heat v.transfer medium into contact with said walls of the exothermic reaction zone.

, 6. The method defined in claim 1, wherein the temperature of said heat transfer medium is readjustedLot the desired value prior to each successive contact. thereof with said walls of the l exothermic reaction zone.

7. An apparatus 'of the class described comprising an endothermic reaction zone and an exo- `thermic reaction zone, both having heat-conductive walls, means for contacting the wallsof said exothermic zone with a owing lm of a heat transfer liquid at a temperature closely approaching its vaporization point, means for con`- tacting vapors of said liquid with the walls of said endothermic zone, means for collecting condensate condensed on the last-named walls, and means for returning regulated quantities of said condensate into contact with the walls of the exothermlc zone.

8. The apparatus as defined in claim 7 further characterized in the provision of means for increasing the heat content of said vapors prior to their contact with the walls of the endothermic zone.

9. An apparatus of theclass described comprising an endothermic reaction zone and an exothermic reaction zone, both having heat-conductive walls, means for contacting the walls of said exothermic zone with a owing lm of a heat transfer liquid at a temperature closely approaching its vaporization point, whereby vapors are evolved from said liquid, said endothermic and exothermic reaction zones being enclosed in a common vessel whereby vapors evolved from said liquid contact with and condense on the walls of the endothermic zone, an accumulator exterior of said vessel and means for supplying thereto condensate formed on the last-named walls, and means for returning liquid from the accumulator to said vessel and into contact with the walls of the exothermic zone.

CHARLES L. THOMAS. 

